Aggregated dyes for radiation-sensitive elements

ABSTRACT

A dispersion comprising an aqueous medium having dispersed therein an aggregated dye of the Formula (I):                    
     wherein X is oxygen or sulfur; R 1 -R 4  each independently represent an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group; L 1 , L 2  and L 3  each independently represent substituted or unsubstituted methine groups; M +  represents a proton or an inorganic or organic cation; and n is 0, 1, 2 or 3 and wherein the aggregated dye in the dispersion has an absorption half bandwidth of less than 55 nm.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional of application Ser. No. 08/565,480, filed Nov. 30,1995, now U.S Pat. No. 6,183,944.

FIELD OF THE INVENTION

This invention relates to a dispersion of an aggregated dye, a methodfor preparing said dispersion and a radiation-sensitive elementcontaining said aggregated dye.

BACKGROUND OF THE INVENTION

Radiation-sensitive materials, including light-sensitive materials, suchas photographic materials, may utilize filter dyes for a variety ofpurposes. Filter dyes may be used to adjust the speed of aradiation-sensitive layer; they may be used as absorber dyes to increaseimage sharpness of a radiation-sensitive layer; they may be used asantihalation dyes to reduce halation; they may be used to reduce theamount or intensity of radiation from reaching one or moreradiation-sensitive layers, and they may also be used to preventradiation of a specific wavelength or range of wavelengths from reachingone or more of the radiation-sensitive layers in a radiation-sensitiveelement. For each of these uses, the filter dye(s) may be located in anynumber of layers of a radiation-sensitive element, depending on thespecific requirements of the element and the dye, and on the manner inwhich the element is to be exposed. The amount of filter dyes usedvaries widely, but they are preferably present in amounts sufficient toalter in some way the response of the element to radiation. Filter dyesmay be located in a layer above a radiation-sensitive layer, in aradiation-sensitive layer, in a layer below a radiation-sensitive layer,or in a layer on the opposite side of the support from aradiation-sensitive layer.

Photographic materials often contain layers sensitized to differentregions of the spectrum, such as red, blue, green, ultraviolet,infrared, X-ray, to name a few. A typical color photographic elementcontains a layer sensitized to each of the three primary regions of thevisible spectrum, i.e., blue, green, and red. Silver halide used inthese materials has an intrinsic sensitivity to blue light. Increasedsensitivity to blue light, along with sensitivity to green light or redlight, is imparted through the use of various sensitizing dyes adsorbedto the silver halide grains. Sensitized silver halide retains itsintrinsic sensitivity to blue light.

There are numerous applications for which filtration or absorbance ofvery specific regions of light are highly desirable. Some of theseapplications, such as yellow filter dyes and magenta trimmer dyes,require non-diffusing dyes which may be coated in a layer specificmanner to prevent specific wavelengths of light from reaching specificlayers of the film during exposure. These dyes must have sharp-cuttingbathochromic absorbance features on the bathochromic side to preventlight punch through without adversely affecting the speed of theunderlying emulsions. Depending on the location of these filter layersrelative to the sensitized silver halide emulsion layers, it would alsobe desirable to have non-diffusing, layer specific filter dyes withabsorption spectra which are sharp-cutting on the hypsochromic edge aswell as the bathochromic edge. Such dyes are sometimes known as “fingerfilters”. Preferably these dyes should exhibit high extinctioncoefficients, narrow half bandwidths and sharp cutting hypsochromic andbathochromic absorption envelopes when incorporated into photographicelements. Typically, to achieve these properties, solutions ofdissolved, monomeric dyes (non-aggregated) have been incorporated. Dyesintroduced by this method cannot be coated in a layer specific mannerwithout the use of mordants, and therefore they often wander intoadjacent layers and can cause problems such as speed loss or stain.Solubilized monomeric dyes may be mordanted to prevent wandering throughadjacent layers. While the use of polymeric mordants can prevent dyewandering, such mordants aggravate the stain problem encountered whenthe dye remains in the element through processing.

Dyes with a high extinction coefficient allow maximum light absorptionusing a minimum amount of dye. Lower requisite dye laydown reduces thecost of light filtration and produces fewer processing by-products.Lower dye laydowns may also result in reduced dye stain in shortduration processes.

Finger filters such as described above are highly desirable for otheruses such as protecting silver halide sensitized emulsions from exposureby safelights. Such dyes must have absorbance spectra with highextinction coefficients and narrow half bandwidths, and sharp cuttingabsorbance envelopes to efficiently absorb light in the narrowsafelight-emitting region without adversely affecting the speed of thesensitized silver halide emulsions. This affords protection for thesensitized emulsion from exposure by light in the safelight's spectralregion. Useful absorbance maxima for safelight dyes include, but are notrestricted to 490 nm and 590 nm.

Similar properties are required for infrared absorbing filter dyes.Laser-exposed radiation-sensitive elements require high efficiency lightabsorbance at the wavelength of laser emission. Unwanted absorbance frombroadly absorbing dyes reduces the efficiency of light capture at thelaser emission wavelength, and requires the use of larger amounts of dyeto adequately cover the desired spectral region. In photographicelements, unwanted absorbance may also cause speed losses in adjacentsilver halide sensitized layers if the photographic element has multiplesensitized layers present. Useful finger filter absorbance maxima forabsorbing laser and phosphor emissions include but are not restricted to790 nm, 633 nm, 670 nm, 545 nm and 488 nm. [Laserablation/non-photographic]

In some photographic elements it is necessary to provide lightfiltration or antihalation at deep cyan and infrared wavelengths.Typically such protection has been achieved using water soluble dyes ormilled solid particle dyes. Typically, water soluble monomeric dyes canprovide relatively sharp, high extinction absorbance, but are prone tointerlayer wandering. Solid particle dispersions of typical cyan filterdyes are broad absorbing, see for example U.S. Pat. No. 4,770,984, andoften weakly absorbing at 700 nm.

One common use for filter dyes is in silver halide light sensitivephotographic elements. If, prior to processing, blue light reaches alayer containing silver halide which has been sensitized to a region ofthe spectrum other than blue, the silver halide grains exposed to theblue light, by virtue of their intrinsic sensitivity to blue light,would be rendered developable. This would result in a false rendition ofthe image information being recorded in the photographic element. It istherefore a common practice to include in the photographic element amaterial that filters blue light. This blue-absorbing material can belocated anywhere in the element where it is desirable to filter bluelight. In a color photographic element that has layers sensitized toeach of the primary colors, it is common to have the blue-sensitizedlayer closest to the exposure source and to interpose a blue-absorbing,or yellow filter layer between the blue-sensitized layer and the green-and red-sensitized layers.

Another common use for filter dyes is to filter or trim portions of theUV, visible or infrared spectral regions to prevent unwanted wavelengthsof light from reaching sensitized emulsions. Just as yellow filter dyesprevent false color rendition from the exposure of emulsions sensitizedto a region of the spectrum other than blue, UV, magenta, cyan andinfrared filter dyes can prevent false color rendition by shieldingsensitized emulsion layers from exposure to specific wavelength regions.One application of this strategy is the use of green-absorbing magentatrimmer dyes. In one type of typical color photographic elementcontaining a layer sensitized to each of the three primary regions ofthe visible spectrum, i.e., blue, green, and red, the green-sensitizedlayer is coated above the red-sensitized layer and below theblue-sensitized layer. Depending on the chosen spectral sensitivitymaxima for the sensitized silver halide layers, there may be a region ofoverlap between the spectral sensitivities of the green and redemulsions. Under such circumstances, green light which is not absorbedby the green-sensitive emulsion can punch through to the red sensitiveemulsion and be absorbed by the leading edge of the red spectralsensitizing dye. This crosstalk between the green and red emulsionsresults in false color rendition. It would, therefore, be highlydesirable to find a green-absorbing filter dye which upon incorporationinto a photographic element would absorb strongly around the spectralmaximum of the green-sensitized emulsion, and possess a sharp cuttingbathochromic absorbance such that there is no appreciable absorbancejust bathochromic to its absorbance maximum. Though the position ofoptimal absorption maximum for a magenta trimmer dye will vary dependingon the photographic element being constructed, it is particularlydesirable in one type of typical color photographic element containing alayer sensitized to each of the three primary regions of the visiblespectrum, i.e., blue, green, and red, that a magenta trimmer dye absorbstrongly at about 550 nm, and possess a sharp cutting bathochromicabsorbance such that there is no appreciable absorbance above about 550nm. Therefore it would be desirable to provide a filter dye for use inphotographic elements that possesses high requisite absorbance in thegreen region of the spectrum below about 550 nm, but little or noabsorbance above about 550 nm, and furthermore does not suffer fromincubative or post process stain problems, and furthermore is not proneto migration in the coated film, but is fully removed upon processing.

One method used to incorporate soluble monomeric filter dyes intophotographic film element layers is to add them as aqueous or alcoholicsolutions. Dyes introduced by this method are generally highly mobileand rapidly diffusing and often wander into other layers of the element,usually with deleterious results. While the use of polymeric mordantscan prevent dye wandering, such mordants aggravate the stain problemencountered when the dye remains in the element through processing.

Filter dyes have also been prepared as conventional dispersions inaqueous gelatin using standard colloid milling or homogenization methodsor as loaded latices. More recently, ball-milling, sand-milling,media-milling and related methods of producing fine particle sizeslurries and suspensions of filter dyes have become standard tools forproducing slurries and dispersions that can readily be used inphotographic melt formulations. Solid particulate filter dyes introducedas dispersions, when coated at sufficiently low pH, can eliminateproblems associated with dye wandering. However, milled, insoluble solidparticulate filter dyes provide relatively low absorption coefficients,requiring that an excessive amount of dye be coated. In addition, thetime and expense involved in preparing serviceable solid particulatefilter dye dispersions by milling techniques are a deterrent to theiruse, especially in large volume applications. It is therefore desirableto provide dye dispersions that do not necessarily require mechanicalmilling before use and that do not wander but that wash out easilyduring processing leaving little or no residual stain. It is alsodesirable that such filter dye dispersions provide high light absorptionefficiencies with sharp-cutting absorbance peaks. One method ofobtaining these desirable dye features in solid particulate dispersionsof oxonol filter dyes was described by Texter (U.S. Pat. No. 5,274,109and U.S. Pat. No. 5,326,687). Texter describes a process by whichpyrazolone oxonol dyes are microprecipitated under strictly controlledpH conditions to produce absorbance spectra which are narrow,bathochromic and sharp cutting on the long wavelength side relative totheir corresponding milled solid particulate dispersions. Thistechnique, however, is impractical for large volume applications.

PROBLEM TO BE SOLVED BY THE INVENTION

It is therefore desirable to have a filter dye which has a highextinction coefficient, narrow halfbandwidth, sharp cutting on both thehypsochromic and bathochromic edge, and capable of being substantiallycompletely removed or rendered colorless on process of an exposedradiation-sensitive element comprising said dye. It is also desirable tohave a method for preparing a dispersion of a filter dye that issuitable for high volume manufacture.

SUMMARY OF THE INVENTION

One object of this invention is to provide a filter dye which whendispersed and aggregated in a hydrophilic colloid such as gelatin,possesses a spectral absorbance maximum bathochromically shifted andexhibits an unusually high extinction coefficient and an exceptionallynarrow halfbandwidth relative to its non-aggregated solution absorbancespectrum.

Another object of this invention is to provide a filter dye which whendispersed and aggregated in a hydrophilic colloid such as gelatin,possesses narrow absorption bands exhibiting an especially sharp-cuttingabsorbance envelope on the short and long wavelength edges.

Another object of this invention is to provide a filter dye which whendispersed and aggregated in a hydrophilic colloid such as gelatin,exhibits low dye diffusibility and interlayer wandering.

Another object of this invention is to provide a direct gelatindispersion method allowing easy and reproducible incorporation of theinventive dyes in an aggregated state, with all desirable propertiesintact, into photographic elements without recourse to millingtechniques.

Another object of this invention is to provide a filter dye which whendispersed and aggregated in a hydrophilic colloid such as gelatinexhibits excellent stability at high temperature and humidityconditions.

Another object of the invention is to provide a silver halideradiation-sensitive material containing at least one aggregated dye,incorporated in a hydrophilic colloid layer, which is decolorizedirreversibly by photographic processing and which causes no deleteriouseffects on the silver halide photographic emulsions before or afterprocessing.

A further object of the invention is to provide a silver halideradiation-sensitive material in which a hydrophilic colloid layer isdyed and exhibits excellent decolorizing properties upon photographicprocessing.

Yet another object of the invention is to provide a silver halideradiation-sensitive material in which a hydrophilic colloid layer isdyed and exhibits high absorbance in a portion of the spectral region atits absorbance maximum, but possesses comparatively little absorbancearound 20 nm above its absorbance maximum.

Yet another object of the invention is to provide a silver halideradiation-sensitive material in which a hydrophilic colloid layer isdyed and exhibits high absorbance in a portion of the spectral region atits absorbance maximum, but possesses comparatively little absorbancearound 20 nm below its absorbance maximum.

We have now discovered that certain dyes of Formula I, II and III, setforth below, aggregate when dispersed in an aqueous medium (preferablycontaining a hydrophilic colloid) and provide the advantages set for inthe above objects of the invention. The said dye dispersion can beprepared by dispersing powdered dye or microcrystalline solid dyeparticles in an aqueous medium, preferably containing gelatin or otherhydrophilic colloid, using the methods set forth herein.

One aspect of this invention comprises an aqueous dispersion comprisingan aqueous medium having dispersed therein an aggregated dye ofstructural Formula I:

wherein X is oxygen or sulfur; R¹-R⁴ each independently represent anunsubstituted or substituted alkyl group, an unsubstituted orsubstituted aryl group or an unsubstituted or substituted heteroarylgroup; L¹, L² and L³ each independently represent substituted orunsubstituted methine.groups; M⁺ represents a proton or an inorganic ororganic cation; and n is 0, 1, 2 or 3 and wherein the aggregated dye inthe dispersion has an absorption halfbandwidth of less than 55 nm.

In another preferred embodiment of the invention the aggregated dye ofstructural Formula I is of Formula II:

wherein R¹ to R⁴ and M⁺ are as defined above and R⁵ represents ahydrogen atom or an unsubstituted or substituted alkyl, aryl or acylgroup.

In yet another preferred embodiment of the invention the aggregated dyeof structural Formula I is of Formula III:

wherein R¹ to R⁴, X, M⁺ and R⁵ are as defined above.

Still another preferred embodiment of the invention comprises aradiation-sensitive element, such as a photographic element, containingan aggregated dye of structural Formula I, II or III.

Yet another preferred embodiment of the invention comprises a method ofpreparing a dispersion which comprises adding a dye of structuralFormula I, II or III to an aqueous medium at a temperature of from about20 to about 100° C. and agitating the mixture for about 5 minutes toabout 48 hours.

ADVANTAGEOUS EFFECTS OF THE INVENTION

This invention provides a dye, useful as a filter dye in aradiation-sensitive element, such as a photographic element, which whendispersed in an aqueous medium, for example aqueous gelatin, dissolvesthen spontaneously aggregates. In some instances, the aggregated dyestate constitutes an unusually well-ordered and thermodynamically stableliquid crystalline phase. A dye in the aggregated state possesses acoated λ_(max) which is substantially bathochromic to that of itsmonomeric non-aggregated state and exhibits exceptionally high coveringpower at its coating λ_(max) Further the aggregated dye exhibitssharp-cutting bathochromic and hypsochromic spectral features absorbingstrongly at its coating λ_(max) while absorbing comparatively littlelight at wavelengths just below or just above its absorbance maximum.Further, the aggregated dye possesses an unusually narrow halfbandwidth.The dyes can be formulated using methods for producing microcrystallinesolid particle dye dispersions (SPD's), or as direct gelatin dispersions(DGD's) for incorporation in a photographic element. In such anenvironment, the spontaneously aggregated dyes exhibit little, if anytendency to wander within the element and upon processing aresubstantially free of post-process stain problems.

DETAILED DESCRIPTION OF THE INVENTION

As noted above, the dispersion of this invention comprises an aggregateddye of Formula I:

wherein X is oxygen or sulfur; R¹-R⁴ each independently represent anunsubstituted or substituted alkyl group, an unsubstituted orsubstituted aryl group or an unsubstituted or substituted heteroarylgroup; L¹, L² and L³ each independently represent substituted orunsubstituted methine groups; M⁺ represents a proton or an inorganic ororganic cation; and n is 0, 1, 2 or 3 and wherein the aggregated dye inthe dispersion has an absorption halfbandwidth of less than 55 nm.

In a preferred embodiment of the invention the aggregated dye ofstructural Formula I is of Formula II:

wherein R¹ to R⁴ and M⁺ are as defined above and R⁵ represents ahydrogen atom or an unsubstituted or substituted alkyl, aryl or acylgroup.

In yet another preferred embodiment of the invention the aggregated dyeof structural Formula I is of Formula III:

wherein R¹ to R⁴ , X and M⁺ are as defined above.

In Formula (I), (II) and (III), illustrative alkyl groups preferablycontain 1 to 6 carbon atoms and include methyl, ethyl, n-propyl,isopropyl, n-butyl, t-butyl, n-hexyl, and isohexyl. Examples of arylgroups include phenyl, naphthyl, anthracenyl, and styryl. Examples ofsubstituted aryl groups include, for example, tolyl, m-chlorophenyl andp-methanesulfonylphenyl, etc- Examples of heteroaryl groups includepyridyl, thienyl, furyl, and pyrrolyl. Examples of acyl groups includeethoxycarbonyl, amido, benzoyl, carboxy and acetyl. M⁺ is preferably H,Na, K, triethyl ammonium or pyridinium.

When reference in this application is made to a substituent “group”,this means that the substituent may itself be substituted orunsubstituted (for example “alkyl group” refers to an unsubstituted orsubstituted alkyl). Generally, unless otherwise specifically stated,substituents on any “groups” referenced herein or where something isstated to be possibly substituted, include the possibility of anygroups, whether substituted or unsubstituted, which do not destroyproperties necessary for the photographic utility. For example, thefilter dyes of this invention should not contain a substituent orcombination of substituents, which render the dye too soluble at coatingpH's, favoring a mobile monomeric dye species instead of the preferredaggregated dye species. It will also be understood throughout thisapplication that reference to a compound of a particular general formulaincludes those compounds of other more specific formula which specificformula falls within the general formula definition.

Examples of substituents on any of the mentioned groups can includeknown substituents, such as: halogen, for example, chloro, fluoro,bromo, iodo; alkoxy, particularly those with 1 to 6 carbon atoms (forexample, methoxy, ethoxy); substituted or unsubstituted alkyl,particularly lower alkyl (for example, methyl, trifluoromethyl); alkenylor thioalkyl (for example, methylthio or ethylthio), particularly eitherof those with I to 6 carbon atoms; substituted and unsubstituted aryl,particularly those having from 6 to 20 carbon atoms (for example,phenyl, naphthyl, anthracenyl or styryl); and substituted orunsubstituted heteroaryl, particularly those having a 5 or 6-memberedring containing 1 to 3 heteroatoms selected from N, O, or S (forexample, pyridyl, thienyl, furyl, pyrrolyl); and others known in theart. Alkyl substituents may specifically include “lower alkyl”, that ishaving from 1 to 6 carbon atoms, for example, methyl, ethyl, and thelike. Further, with regard to any alkyl group, alkylene group or alkenylgroup, it will be understood that these can be branched or unbranchedand include ring structures.

Examples of preferred dyes of this invention are listed below.

TABLE I

Dye R⁶ R⁷ R⁸ R⁹ R¹⁰ R¹¹ M⁺  1 H H H OMe H Me H  2 H H Me OH H H H  4 H HH H OMe Me H    4A H H H H OMe Me Na  5 H H H OH H Me H  7 H H H OMe HEt H  8 H H H H OMe H H    8A H H H H OMe H TEAH  9 H H H H OH H H    9AH H H H OH H PyrH 10 H H H OH H H H 11 H OMe H H H H H   10A H H H OH HH PyrH  10B H H H OH H H TEAH 12 H OMe H H OMe H H 14 H H H Me H Me H 15H H H H Me H H 16 H H H H OMe Me H 17 H H H Me H CONH₂ H 18 H H H Cl HMe H 19 H H H CN H Me H 20 H H H CONH₂ H Et H 21 H H H Me H Et TEAH 22 HH Me H H Me H 23 H H H OMe H COPh TEAH 24 H H H COOH H Et H 25 H H HNHSO₂Me H Me H 26 H H OMe H OMe Me H 27 H H CN H CN Me H 28 H H Cl H HEt H 29 H H COOH H H Me H 30 H OMe OMe H H Me H 31 H OMe H Me H Et H 32H OMe H Me H CONMe₂ H 33 H H Cl OH Cl Et H 34 H CN H H H H H 35 H H H HH Me H

TABLE II

Dye R⁶ R⁷ R⁸ R⁹ R¹⁰ R¹¹ M⁺  3 H H OH H H H H    3A H H OH H H H PyrH  6H H H OH H H H 13 H H H H H H H   13A H H H H H H TEAH 36 H OH H H H HTEAH 37 H H OH OH H H H 38 H H H NHSO₂Me H H TEAH 39 H H OH Me H H TEAH

TABLE III

Dye R⁶ R⁷ R⁸ R⁹ R¹⁰ R¹¹ M⁺ 40 H H H H H H TEAH 41 H H H Cl H H TEAH 42 HH H Me H H TEAH 43 H H H OH H H TEAH 44 H H H NHCOCH₃ H H TEAH 45 H HOMe H H H TEAH 46 H H OMe H H Me TEAH

TABLE III

Dye R⁶ R⁷ R⁸ R⁹ R¹⁰ R¹¹ M⁺ 40 H H H H H H TEAH 41 H H H Cl H H TEAH 42 HH H Me H H TEAH 43 H H H OH H H TEAH 44 H H H NHCOCH₃ H H TEAH 45 H HOMe H H H TEAH 46 H H OMe H H Me TEAH

The dyes of Formulas (I), (II) and (III) can be prepared by synthetictechniques well-known in the art, as illustrated by the syntheticexamples below. Such techniques are further illustrated, for example, in“The Cyanine Dyes and Related Compounds”, Frances Hamer, IntersciencePublishers, 1964.

The dispersions of this invention can be prepared in any of the waysknown in the art (e.g., with the aid of a high-boiling non-polar organicsolvent or in suitable water-miscible solvents such as methyl alcohol ordimethylformamide or the like), but are preferably formulated usingmethods developed for producing solid microcrystalline particles of dye(SPD's) or are more preferably formulated as direct gelatin dispersions(DGD's) as described herein.

A dispersion comprising solid microcrystalline particles of dye (SPD)can be prepared by known methods. Such methods includes forming a slurryof the dye in an aqueous medium comprising water and a surfactant andthe subjecting the slurry to a milling procedure such as ball-milling,sand-milling, media-milling or colloid-milling (preferablymedia-milling). The SPD can then be added to an aqueous mediumcomprising water and a hydrophilic colloid, such as gelatin, for use ina photographic element.

In another preferred embodiment, the dyes may be formulated as a directgelatin dispersion (DGD) wherein the finely powdered dye or aqueousslurry thereof is simply mixed or agitated with aqueous mediumcontaining gelatin (or other hydrophilic colloid) at a temperature of40° C. or higher. This method does not require the use of organicsolvents, surfactants, polymer additives, milling processes, pH controlor the like. It is simpler, faster, more forgiving and more flexiblethan prior processes.

In either of the preferred methods, the dyes may be subjected toelevated temperatures before and/or after gelatin dispersion, but toobtain desirable results, this heat treatment is carried out preferablyafter dispersing in gelatin. The optimal temperature range for preparinggelatin-based dispersions is 40° C.-100° C. but should remain below thedecomposition points of the dyes. The heating time is not especiallycritical as long as the dyes are not decomposed, but in general it is inthe range of 5 minutes to 48 hours. A similar heat treatment may beapplied, if so desired, to dyes prepared as solid particle dispersionsbefore and/or after dispersion in aqueous gelatin to obtain effectiveresults. Furthermore, if so desired, pH and/or ionic strengthadjustments may be utilized to control the solubility and aggregationproperties of dyes prepared using SPD or DGD formulation techniques. Thedirect gelatin dispersion method is advantageous in that it does notnecessarily require the use of organic solvents, surfactants, polymeradditives, milling processes, pH control or the like. A related methoddescribed by Boettcher for preparing concentrated sensitizing dyedispersions in aqueous gelatin (PCT WO 93/23792) is equally effectivewhen applied to the inventive dyes. The entire disclosure of WO 93/23792is incorporated herein by reference.

Solid particle dispersion and direct gelatin dispersion formulations ofthe compound of Formula (I-III) are useful as general purpose filterdyes, alone or in combination with other filter dyes in photographicelements. The dyes formulated as described above possess finite but lowsolubilities and a pronounced tendency to aggregate spontaneously atcoating pH's of 6 or less (generally 4-6) so that they do not interactwith other components of the photographic element. However, they arehighly soluble at processing pH's of 8 or more (generally 8-12), suchthat they are still fully removed during photographic processing.

A particular advantage of the inventive dyes is that in the aggregatedstate, they provide higher covering power at their coating λ_(max) thancomparable known dyes which are insoluble and exist as microcrystallinesolid particles in the photographic medium. This advantage isparticularly important in modern film formats and processing conditions,as filter dyes with high covering power need not be coated at as high acoverage as dyes with lower covering power in order to achieve the samedegree of light filtration. In addition to reducing manufacturing costs,lower levels of coated dyes will reduce the level of dye residue builtup in the processing solutions, and the resulting lower levels ofdissolved dye residue removed from photographic elements will havereduced environmental impact.

A further advantage of dyes of the invention is that they generallypossess absorbance envelopes that are sharper cutting on thebathochromic side than comparable known solid particle dyes such as thestructural analogs disclosed in Agfa U.S. Pat. No. 4,770,984. Thisfeature is especially advantageous when strong light absorbance isrequired in a spectral region up to a specific λ_(max), and maximumlight transmission is required past the specified λ_(max). Such filteror trimmer dyes are especially useful when coated in specific layers ofcolor photographic films to effectively prevent light of a specificwavelength region from exposing radiation-sensitive layers below thelight filtration layer containing the dye, without causing unwantedabsorption of longer wavelength radiation. A green filter dye coateddirectly above a red-sensitive silver halide layer is a particularlyadvantageous example of such absorbance features, and excellentgreen/red speed separation can be realized. In a typical colorphotographic element, it is desirable to have a green-absorbing filterdye which when coated absorbs strongly at wavelengths close to 550 nm,but which absorbs comparatively little at wavelengths greater than 550nm. It should be emphasized that the exact envelope of desirable lightabsorbance for a filter dye, even specifically a green filter dye,varies tremendously from one photographic element to another dependingon the intended purpose of the material. Some photographic elementsmight require a filter dye, such as a green filter dye, which absorbsstrongly up to a wavelength somewhat shorter or longer than 550 nm, butis sharp cutting on the bathochromic side, mostly transmittingwavelengths of light past the desired absorbance λ_(max). The feature ofcoated dye absorbance exhibiting a sharp cutting bathochromic and/orhypsochromic characteristic is fundamentally useful forwavelength-specific light filtration, though the exact wavelength ofdesired spectral shift from absorbance to transmission may be differentfor different photographic materials.

The dyes may be located in any layer of the element where it isdesirable to absorb light, but in photographic elements it isparticularly advantageous to locate them in a layer where they will besolubilized and washed out during processing. Useful amounts of dyerange from 1 to 1000 mg/m². The dye should be present in an amountsufficient to yield an optical density at the absorbance D_(max) in thespectral region of interest before processing of at least 0.10 densityunits and preferably at least 0.50 density units. This optical densitywill generally be less than 5.0 density units for most photographicapplications.

The dyes of the invention can be used as interlayer dyes, trimmer dyes,or antihalation dyes. They can be used to prevent crossover in X-raymaterials as disclosed in U.S. Pat. Nos. 4,900,652 and 4,803,150 andEuropean Patent Application Publication No. 0 391 405, to preventunwanted light from reaching a sensitive emulsion layer of a multicolorphotographic element as disclosed in U.S. Pat. No. 4,988,611, and forother uses as indicated by the absorbance spectrum of the particulardye. The dyes can be used in a separate filter layer or as an intergrainabsorber.

The aggregated dyes of Formula (I-III) are useful for the preparation ofradiation sensitive materials. Such materials are sensitive to radiationsuch as visible light, ultraviolet, infrared, X-ray. The material can bean optical recording medium, such as a CD or other medium sensitive to alaser, light emitting diode, or a more conventional light-sensitivephotographic material.

Another aspect of this invention comprises a radiation sensitive elementcontaining an aggregated dye of Formula (I-III). Preferably, theradiation sensitive element is a photographic element comprising asupport bearing at least one light sensitive hydrophilic colloid layerand at least one other hydrophilic colloid layer. A dye of Formula I, IIor III may be incorporated in a hydrophilic layer of the photographicelement in any known way.

The support of the element of the invention can be any of a number ofwell-known supports for photographic elements as discussed more fullybelow.

The photographic elements made by the method of the present inventioncan be single color elements or multicolor elements. Multicolor elementscontain dye image-forming units sensitive to each of the three primaryregions of the spectrum. Each unit can be comprised of a single emulsionlayer or of multiple emulsion layers sensitive to a given region of thespectrum. The layers of the element, including the layers of theimage-forming units, can be arranged in various orders as known in theart. In an alternative format, the emulsions sensitive to each of thethree primary regions of the spectrum can be disposed as a singlesegmented layer.

A typical multicolor photographic element comprises a support bearing acyan dye image-forming unit comprised of at least one red-sensitivesilver halide emulsion layer having associated therewith at least onecyan dye-forming coupler, a magenta dye image-forming unit comprising atleast one green-sensitive silver halide emulsion layer having associatedtherewith at least one magenta dye-forming coupler, and a yellow dyeimage-forming unit comprising at least one blue-sensitive silver halideemulsion layer having associated therewith at least one yellowdye-forming coupler. The element can contain additional layers, such asfilter layers, interlayers, overcoat layers, subbing layers, and thelike. All of these can be coated on a support which can be transparentor reflective (for example, a paper support).

Photographic elements of the present invention may also usefully includea magnetic recording material as described in Research Disclosure, Item34390, November 1992, or a transparent magnetic recording layer such asa layer containing magnetic particles on the underside of a transparentsupport as in U.S. Pat. No. 4,279,945 and U.S. Pat. No. 4,302,523. Theelement typically will have a total thickness (excluding the support) offrom 5 to 30 microns. While the order of the color sensitive layers canbe varied, they will normally be red-sensitive, green-sensitive andblue-sensitive, in that order on a transparent support, (that is, bluesensitive furthest from the support) and the reverse order on areflective support being typical.

The present invention also contemplates the use of photographic elementsof the present invention in what are often referred to as single usecameras (or “film with lens” units). These cameras are sold with filmpreloaded in them and the entire camera is returned to a processor withthe exposed film remaining inside the camera. Such cameras may haveglass or plastic lenses through which the photographic element isexposed.

In the following discussion of suitable materials for use in elements ofthis invention, reference will be made to Research Disclosure, September1994, Number 365, Item 36544, which will be identified hereafter by theterm “Research Disclosure I.” The Sections hereafter referred to areSections of the Research Disclosure I unless otherwise indicated. AllResearch Disclosures referenced are published by Kenneth MasonPublications, Ltd., Dudley Annex, 12a North Street, Emsworth, HampshireP010 7DQ, ENGLAND. The foregoing references and all other referencescited in this application, are incorporated herein by reference.

The silver halide emulsions employed in the photographic elements of thepresent invention may be negative-working, such as surface-sensitiveemulsions or unfogged internal latent image forming emulsions, orpositive working emulsions of internal latent image forming emulsions(that are either fogged in the element or fogged during processing).Suitable emulsions and their preparation as well as methods of chemicaland spectral sensitization are described in Sections I through V. Colormaterials and development modifiers are described in Sections V throughXX. Vehicles which can be used in the photographic elements aredescribed in Section II, and various additives such as brighteners,antifoggants, stabilizers, light absorbing and scattering materials,hardeners, coating aids, plasticizers, lubricants and matting agents aredescribed, for example, in Sections VI through XIII. Manufacturingmethods are described in all of the sections, layer arrangementsparticularly in Section XI, exposure alternatives in Section XVI, andprocessing methods and agents in Sections XIX and XX.

With negative working silver halide a negative image can be formed.Optionally a positive (or reversal) image can be formed although anegative image is typically first formed.

The photographic elements of the present invention may also use coloredcouplers (e.g., to adjust levels of interlayer correction) and maskingcouplers such as those described in EP 213 490; Japanese PublishedApplication 58-172,647; U.S. Pat. No. 2,983,608; German Application DE2,706,117C; U.K. Pat. No. 1,530,272; Japanese Application A-113935; U.S.Pat. No. 4,070,191 and German Application DE 2,643,965. The maskingcouplers may be shifted or blocked.

The photographic elements may also contain materials that accelerate orotherwise modify the processing steps of bleaching or fixing to improvethe quality of the image. Bleach accelerators described in EP 193 389;EP 301 477; U.S. Pat. No. 4,163,669; U.S. Pat. No. 4,865,956; and U.S.Pat. No. 4,923,784 are particularly useful. Also contemplated is the useof nucleating agents, development accelerators or their precursors (UKPatent 2,097,140; U.K. Patent 2,131,188); electron transfer agents (U.S.Pat. No. 4,859,578; U.S. Pat. No. 4,912,025); antifogging and anticolor-mixing agents such as derivatives of hydroquinones, aminophenols,amines, gallic acid; catechol; ascorbic acid; hydrazides;sulfonamidophenols; and non color-forming couplers.

The elements may also contain filter dye layers comprising colloidalsilver sol or yellow and/or magenta filter dyes and/or antihalation dyes(particularly in an undercoat beneath all light sensitive layers or inthe side of the support opposite that on which all light sensitivelayers are located) formulated either as oil-in-water dispersions, latexdispersions, solid particle dispersions, or as direct gelatindispersions. Additionally, they may be used with “smearing” couplers(e.g., as described in U.S. Pat. No. 4,366,237; EP 096 570; U.S. Pat.No. 4,420,556; and U.S. Pat. No. 4,543,323.) Also, the couplers may beblocked or coated in protected form as described, for example, inJapanese Application 61/258,249 or U.S. Pat. No. 5,019,492.

The photographic elements may further contain other image-modifyingcompounds such as “Developer Inhibitor-Releasing” compounds (DIR's).Useful additional DIR's for elements of the present invention, are knownin the art and examples are described in U.S. Pat. Nos. 3,137,578;3,148,022; 3,148,062; 3,227,554; 3,384,657; 3,379,529; 3,615,506;3,617,291; 3,620,746; 3,701,783; 3,733,201; 4,049,455; 4,095,984;4,126,459; 4,149,886; 4,150,228; 4,211,562; 4,248,962; 4,259,437;4,362,878; 4,409,323; 4,477,563; 4,782,012; 4,962,018; 4,500,634;4,579,816; 4,607,004; 4,618,571; 4,678,739; 4,746,600; 4,746,601;4,791,049; 4,857,447; 4,865,959; 4,880,342; 4,886,736; 4,937,179;4,946,767; 4,948,716; 4,952,485; 4,956,269; 4,959,299; 4,966,835;4,985,336 as well as in patent publications GB 1,560,240; GB 2,007,662;GB 2,032,914; GB 2,099,167; DE 2,842,063, DE 2,937,127; DE 3,636,824; DE3,644,416 as well as the following European Patent Publications:272,573; 335,319; 336,411; 346, 899; 362, 870; 365,252; 365,346;373,382; 376,212; 377,463; 378,236; 384,670; 396,486; 401,612; 401,613.

DIR compounds are also disclosed in “Developer-Inhibitor-Releasing (DIR)Couplers for Color Photography,” C. R. Barr, J. R. Thirtle and P. W.Vittum in Photographic Science and Engineering, Vol. 13, p. 174 (1969),incorporated herein by reference.

It is also contemplated that the concepts of the present invention maybe employed to obtain reflection color prints as described in ResearchDisclosure, November 1979, Item 18716, available from Kenneth MasonPublications, Ltd, Dudley Annex, 12a North Street, Emsworth, HampshireP0101 7DQ, England, incorporated herein by reference. The emulsions andmaterials to form elements of the present invention, may be coated on pHadjusted support as described in U.S. Pat. No. 4,917,994; with epoxysolvents (EP 0 164 961); with additional stabilizers (as described, forexample, in U.S. Pat. No. 4,346,165; U.S. Pat. No. 4,540,653 and U.S.Pat. No. 4,906,559); with ballasted chelating agents such as those inU.S. Pat. No. 4,994,359 to reduce sensitivity to polyvalent cations suchas calcium; and with stain reducing compounds such as described in U.S.Pat. No. 5,068,171 and U.S. Pat. No. 5,096,805. Other compounds usefulin the elements of the invention are disclosed in Japanese PublishedApplications 83-09,959; 83-62,586; 90-072,629, 90-072,630; 90-072,632;90-072,633; 90-072,634; 90-077,822; 90-078,229; 90-078,230; 90-079,336;90-079,338; 90-079,690; 90-079,691; 90-080,487; 90-080,489; 90-080,490;90-080,491; 90-080,492; 90-080,494; 90-085,928; 90-086,669; 90-086,670;90-087,361; 90-087,362; 90-087,363; 90-087,364; 90-088,096; 90-088,097;90-093,662; 90-093,663; 90-093,664; 90-093,665; 90-093,666; 90-093,668;90-094,055; 90-094,056; 90-101,937; 90-103,409; 90-151,577.

The silver halide used in the photographic elements may be silveriodobromide, silver bromide, silver chloride, silver chlorobromide,silver chloroiodobromide, and the like. For example, the silver halideused in the photographic elements of the present invention may containat least 90% silver chloride or more (for example, at least 95%, 98%,99% or 100% silver chloride). In the case of such high chloride silverhalide emulsions, some silver bromide may be present but typicallysubstantially no silver iodide. Substantially no silver iodide means theiodide concentration would be no more than 1%, and preferably less than0.5 or 0.1%. In particular, in such a case the possibility is alsocontemplated that the silver chloride could be treated with a bromidesource to increase its sensitivity, although the bulk concentration ofbromide in the resulting emulsion will typically be no more than about 2to 2.5% and preferably between about 0.6 to 1.2% (the remainder beingsilver chloride). The foregoing % figures are mole %.

The type of silver halide grains preferably include polymorphic, cubic,and octahedral. The grain size of the silver halide may have anydistribution known to be useful in photographic compositions, and may beeither polydipersed or monodispersed.

Tabular grain silver halide emulsions may also be used. Tabular grainsare those with two parallel major faces each clearly larger than anyremaining grain face and tabular grain emulsions are those in which thetabular grains account for at least 30 percent, more typically at least50 percent, preferably >70 percent and optimally >90 percent of totalgrain projected area. The tabular grains can account for substantiallyall (>97 percent) of total grain projected area. The tabular grainemulsions can be high aspect ratio tabular grain emulsions—i.e.,ECD/t >8, where ECD is the diameter of a circle having an area equal tograin projected area and t is tabular grain thickness; intermediateaspect ratio tabular grain emulsions—i.e., ECD/t=5 to 8; or low aspectratio tabular grain emulsions—i.e., ECD/t=2 to 5. The emulsionstypically exhibit high tabularity (T), where T (i.e., ECD/t²) >25 andECD and t are both measured in micrometers (μm). The tabular grains canbe of any thickness compatible with achieving an aim average aspectratio and/or average tabularity of the tabular grain emulsion.Preferably the tabular grains satisfying projected area requirements arethose having thicknesses of <0.3 μm, thin (<0.2 μm) tabular grains beingspecifically preferred and ultrathin (<0.07 μm) tabular grains beingcontemplated for maximum tabular grain performance enhancements. Whenthe native blue absorption of iodohalide tabular grains is relied uponfor blue speed, thicker tabular grains, typically up to 0.5 μm inthickness, are contemplated.

High iodide tabular grain emulsions are illustrated by House U.S. Pat.No. 4,490,458, Maskasky U.S. Pat. No. 4,459,353 and Yagi et al EPO 0 410410.

Tabular grains formed of silver halide(s) that form a face centeredcubic (rock salt type) crystal lattice structure can have either {100}or {111} major faces. Emulsions containing {111} major face tabulargrains, including those with controlled grain dispersities, halidedistributions, twin plane spacing, edge structures and graindislocations as well as adsorbed {111} grain face stabilizers, areillustrated in those references cited in Research Disclosure I, SectionI.B.(3) (page 503).

The silver halide grains to be used in the invention may be preparedaccording to methods known in the art, such as those described inResearch Disclosire I and James, The Theory of the Photographic Process.These include methods such as ammoniacal emulsion making, neutral oracidic emulsion making, and others known in the art. These methodsgenerally involve mixing a water soluble silver salt with a watersoluble halide salt in the presence of a protective colloid, andcontrolling the temperature, pAg, pH values, etc, at suitable valuesduring formation of the silver halide by precipitation.

The silver halide to be used in the invention may be advantageouslysubjected to chemical sensitization with noble metal (for example, gold)sensitizers, middle chalcogen (for example, sulfur) sensitizers,reduction sensitizers and others known in the art. Compounds andtechniques useful for chemical sensitization of silver halide are knownin the art and described in Research Disclosure I and the referencescited therein.

The photographic elements of the present invention, as is typical,provide the silver halide in the form of an emulsion. Photographicemulsions generally include a vehicle for coating the emulsion as alayer of a photographic element. Useful vehicles include both naturallyoccurring substances such as proteins, protein derivatives, cellulosederivatives (e.g., cellulose esters), gelatin (e.g., alkali-treatedgelatin such as cattle bone or hide gelatin, or acid treated gelatinsuch as pigskin gelatin), gelatin derivatives (e.g., acetylated gelatin,phthalated gelatin, and the like), and others as described in ResearchDisclosure I. Also useful as vehicles or vehicle extenders arehydrophilic water-permeable colloids. These include synthetic polymericpeptizers, carriers, and/or binders such as poly(vinyl alcohol),polyvinyl lactams), acrylamide polymers, polyvinyl acetals, polymers ofalkyl and sulfoalkyl acrylates and methacrylates, hydrolyzed polyvinylacetates, polyamides, polyvinyl pyridine, methacrylamide copolymers, andthe like, as described in Research Disclosure I. The vehicle can bepresent in the emulsion in any amount useful in photographic emulsions.The emulsion can also include any of the addenda known to be useful inphotographic emulsions. These include chemical sensitizers, such asactive gelatin, sulfur, selenium, tellurium, gold, platinum, palladium,iridium, osmium, rhenium, phosphorous, or combinations thereof. Chemicalsensitization is generally carried out at pAg levels of from 5 to 10, pHlevels of from 5 to 8, and temperatures of from 30 to 80° C., asdescribed in Research Disclosure I, Section IV (pages 510-511) and thereferences cited therein.

The silver halide may be sensitized by sensitizing dyes by any methodknown in the art, such as described in Research Disclosure I. The dyemay be added to an emulsion of the silver halide grains and ahydrophilic colloid at any time prior to (e.g., during or after chemicalsensitization) or simultaneous with the coating of the emulsion on aphotographic element. The dyes may, for example, be added as a solutionin water or an alcohol. The dye/silver halide emulsion may be mixed witha dispersion of color image-forming coupler immediately before coatingor in advance of coating (for example, 2 hours).

Photographic elements of the present invention are preferably imagewiseexposed using any of the known techniques, including those described inResearch Disclosure I, section XVI. This typically involves exposure tolight in the visible region of the spectrum, and typically such exposureis of a live image through a lens, although exposure can also beexposure to a stored image (such as a computer stored image) by means oflight emitting devices (such as light emitting diodes, CRT and thelike).

Photographic elements comprising the composition of the invention can beprocessed in any of a number of well-known photographic processesutilizing any of a number of well-known processing compositions,described, for example, in Research Disclosure I, or in T.H. James,editor, The Theory of the Photographic Process, 4th Edition, Macmillan,New York, 1977. In the case of processing a negative working element,the element is treated with a color developer (that is one which willform the colored image dyes with the color couplers), and then with aoxidizer and a solvent to remove silver and silver halide. In the caseof processing a reversal color element, the element is first treatedwith a black and white developer (that is, a developer which does notform colored dyes with the coupler compounds) followed by a treatment tofog silver halide (usually chemical fogging or light fogging), followedby treatment with a color developer. Preferred color developing agentsare p-phenylenediamines. Especially preferred are:

4-amino N,N-diethylaniline hydrochloride,

4-amino-3-methyl-N,N-diethylaniline hydrochloride,

4-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido) ethylanilinesesquisulfate hydrate,

4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl) aniline sulfate,

4-amino-3-β-(methanesulfonamido) ethyl-N, N-diethylaniline hydrochlorideand

4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene sulfonicacid.

Development is followed by bleach-fixing, to remove silver or silverhalide, washing and drying.

Synthesis of Dye 1

3-methyl glutacondialdehydedianil hydrobromide (6.6 g, 19 mmol) wasadded portionwise to a solution of 4-methoxyphenylbarbituric acid (9.6g, 41 mmol) in 150 mL pyridine at 80° C. The blue mixture was heated at80° C. for 30 min, then allowed to cool to 25° C. The precipitated dyewas collected by filtration and washed with acetonitrile. The collectedsolid was suspended in 300 mL methanol and stirred while 100 mLconcentrated HCl was added over 10 min, and the resulting slurry wasallowed to stir at 25° C. for 30 min. The dye was collected byfiltration and dried. Isolated 6.2 g (46%) of Dye 1 as a black solid.All analytical data were consistent with the structure.

Synthesis of Dye 8

Glutacondialdehydedianil hydrochloride (7.3 g, 26 mmol) was addedportionwise to a solution of 3-methoxyphenylbarbituric acid (12.0 g, 51mmol) and triethylamine (7.8 g, 77 mmol) in 300 mL ethanol at 25° C. Themixture was heated to reflux and held for 30 min. A blue solidprecipitated from the hot reaction mixture. The mixture was then allowedto cool to 25° C., and the precipitated dye was collected by filtrationand washed with ethanol. The collected solid was suspended in 250 mLethanol and heated to reflux while 3 mL concentrated HCl was added over5 min. The resulting slurry was heated at reflux for 10 min, thenallowed to cool to 25° C. The dye was collected by filtration, washedwith methanol and dried. Isolated 11.3 g (84%) of Dye 8 as a dark solid.All analytical data were consistent with the structure.

EXPERIMENTAL EXAMPLES Example A Microcrystalline Dye Slurry (MDS)Formulation

Dyes were formulated as aqueous microcrystalline dispersions of 0.2microns mean particle size by ball-milling according to the followingprocedure. Water (22.0 g) and a 10.0% solution of Triton X-200®, analkyl aryl polyether sulfonate surfactant available from Rohm and Haas,(1.0 g) were placed in a 120 mL screw-capped bottle. A 1.0 g sample ofdye was added to this solution. Zirconium oxide beads (60 mL, 1.8 mmdiameter) were added and the container with the cap tightly secured wasplaced in a mill and the contents milled for four days. The resultingmixture was then filtered to remove the zirconium oxide beads. Theresulting aqueous microcrystalline dye slurries will be referred to inthe following examples as MDS's.

Example B Solid Particle Dispersion (SPD) Formulation

Aqueous gelatin dispersions of the above MDS's were prepared as follows.The vessel containing the dye MDS was removed and the requisite weightof dye slurry was added to a 12.5% aqueous gelatin solution (18.0 g) at45° C. This mixture was then diluted with water to a weight of 88.87 g.,yielding the final dye dispersion. In the subsequent experimentalsections gelatin-containing dye dispersions prepared in this manner willbe referred to as solid particle dispersions (SPD's). The term “SPD” isused throughout simply to denote dye dispersions which have beenformulated using well known milling techniques normally used forpreparing solid particle microcrystalline dye dispersions. This does notimply that the physical state of the dye prepared in this manner isexclusively microcrystalline in nature.

Example C Direct Gelatin Dispersion (DGD) Formulation

Nominally 1.42500 g H₂O then 0.07500 g deionized gelatin were weighedinto screw-topped glass vials and allowed to soak at 25° C. for at least30 minutes. The swollen gelatin was then melted at 50° C. for 15 minuteswith agitation. The gelatin solution was cooled to 25° C., thenrefrigerated at 5° C. to set. Nominally 1.49700 g H2O was then added ontop of the set gelatin followed by 0.00300 g of powdered dye. The dyepowder was thoroughly wetted and dispersed in the water layer byagitation and then allowed to stand at 25° C. for 17 hours. The sampleswere then heated to 60° C. in a water bath for 2 hours and mixed withintermittent agitation. The samples were subsequently cooled to 39.0° C.over a period of approximately 1 hour and maintained at this temperatureuntil measurement. In the subsequent experimental sections dispersionsprepared in this manner will be referred to as DGD's.

Example 1 Absorption Wavelength (μ_(max)), Halfbandwidth (Hbw) and MolarExtinction Coefficients (ε_(max)) of Wet Dye DGD's.

Direct gelatin dispersions (DGD's) of Dyes 1-16 and Comparative Dyes A-Dwere prepared as described in Example C. Aliquots of each dispersion,held at 39° C., were transferred to 0.0032 cm pathlength glass cells andtheir absorption spectra measured at 25° C. Solutions of Dyes 1-16 andComparative Dyes A-D were prepared in a suitable organic solvent(methanol or methanol with added triethylamine unless otherwise noted)and their absorption spectra measured at 25° C. The extinctioncoefficients were calculated according to Beer's Law, and halfbandwidths (Hbw) measured. The data are summarized in Table V.

TABLE V ε_(max) soln. Hbw λ_(max) ε_(max) DGD Hbw λ_(max) soln. (mol⁻¹|cm⁻¹) soln. DGD (mol⁻¹| cm⁻¹) DGD Dye (nm) ×10⁵ (nm) (nm) ×10⁵ (nm) 1611 1.81 34 793 8.19 18 2 587 1.92 38 738 6.97 19 3 488 1.12 29 558 5.1812 3A 488 1.15 29 558 5.82 12 4 609 1.63 38 779 2.83 24 4A 609 1.60 38778 3.89 16 5 609 1.42 38 790 5.29 19 6 488 1.32 30 555 3.59 17 7 6151.69 35 785 2.82 17 8 586 1.71 39 721 3.58 40 8A 586 1.73 39 721 3.89 429 587 1.48 36 739 3.22 35 9A 587 1.48 36 740 4.96 37 10 587 1.86 36 7174.01 46 10A 587 1.86 36 762 2.42 50 10B 587 1.86 36 717 3.54 46 11 5861.79 39 755 2.45 30 12 586 2.25 35 758 2.83 29 13 586 1.95 36 554 1.8815 13A 586 1.95 36 549 1.79 18 14 609 1.86 38 792 6.74 20 15 586 1.90 39723 3.02 41 16 611 2.01 35 771 6.55 48 A 586 1.69 39 682 1.56 75 Aa 5861.70 39 686 1.44 75 B 586 1.95 37 709 2.10 58 C 587 1.76 39 586 0.77 121D 587 2.10 36 682 1.56 77

The above results demonstrate that the direct in dispersions containingthe inventive dyes in an gated state exhibit bathochromically shiftedlonger wavelength absorption maxima relative to their solution(non-aggregated) absorption maxima. Moreover, the inventive aggregateddyes as DGD's are comparable or superior in both Hbw and extinctioncoefficient to their solution (non-aggregated) counterparts. Moreover,as DGD's the inventive dyes are far superior in both Hbw and extinctioncoefficient to the comparative dyes A to D.

COMPARATIVE DYES Comparative Dye A

Comparative Dye Aa

Comparative Dye B

Comparative Dye C

Comparative Dye D

Example 2 Spectral Shape of Wet Dye DGD's.

Direct gelatin dispersions (DGD's) of Dyes 1-16 and Comparative Dyes A-Dwere prepared as described in Example C. Aliquots of each dispersion,held at 39° C., were transferred to 0.0032 cm pathlength glass cells andtheir absorption spectra measured at 25° C. as wet gelatin films. Theratio of each dye's optical density at λ_(max) (D_(max)) to opticaldensity (O.D.) at λ_(max)+20 nm was calculated. The ratio of each dye'soptical density at λ_(max) (D_(max)) to optical density (O.D.) atλ_(max)−20 nm was also calculated. These ratios are a measure ofspectral band sharpness. Dyes with higher ratios possess sharper cuttingspectral absorption envelopes which are desirable for lightfiltration/absorption applications. The data are summarized in Table VI.

TABLE VI λ_(max) D_(max)/O.D. at D_(max)/O.D. at Dye DGD_(wet)(nm)λ_(max) + 20 nm λ_(max) − 20 nm 1 794 20.3 3.43 2 738 27.2 2.98 3 558321 5.83 3A 558 158 6.70 4 788 4.81 2.48 4A 788 15.0 4.14 5 790 21.93.69 6 554 68.5 3.61 7 782 20.9 3.74 8 722 2.48 1.78 8A 722 2.50 2.00 9738 3.20 2.09 9A 740 2.87 1.97 10 717 2.32 1.55 10A 762 2.18 1.48 10B716 2.24 1.62 11 750 3.31 2.05 12 758 6.06 2.24 13 554 31.5 3.79 13A 54930.9 3.22 14 792 7.29 3.68 15 722 2.47 1.77 16 774 10.2 1.67 A 682 1.391.17 Aa 684 1.53 1.24 B 710 1.96 1.25 C 586 1.48 1.43 D 682 1.50 1.19

The data clearly demonstrate that the inventive dyes 1-16 whenaggregated in aqueous gelatin possess absorption spectra withsignificantly sharper hypsochromic and bathochromic edges relative tothe comparative dyes A to D. Moreover, these useful spectral featuresare largely retained in dried-down gelatin films and layers.

Example 3 Spectral Properties of Wet Gelatin Layers Containing DyesAdded in the Powdered or Microcrystalline State

Each of Dyes 1, 3, 8, 10, 11, 15 and Comparative Dyes A and D in thepowdered state were dispersed directly in aqueous gelatin as describedin Example C. The same dyes, formulated as aqueous microcrystalline dyedispersions (MDS's) in accordance with Example A, were also dispersed inaqueous gelatin at comparable concentrations under identical conditions.Solution aliquots of each dye dispersion were transferred to 0.0032 cmpathlength glass cells and their absorption maxima measured at 25° C. aswet gelatin films. The corresponding extinction coefficients (ε_(max))were calculated using Beer's law, and half bandwidths (Hbw) measured.The data are compared in Table VII, where the qualifers “powder” and“MDS” denote the original physical state of the dye before mixing withgelatin.

TABLE VII λ_(max) λ_(max) Hbw Hbw ε_(max) powder ε_(max) MDS powder MDSpowder MDS (mol⁻¹| cm⁻¹⁾ (mol⁻¹| cm⁻¹) Dye (nm) (nm) (nm) (nm) ×10⁵ ×10⁵1 793 793 18 18 8.19 4.63 3 558 558 12 13 5.18 3.80 8 721 721 40 41 3.584.14 10 717 715 46 48 4.01 1.99 11 755 755 30 30 2.45 2.37 15 723 724 4141 3.02 2.36 A 682 680 75 80 1.56 1.39 D 682 681 77 80 1.56 1.24

The above data demonstrate that excellent results may be obtained fromwet aqueous gelatin dispersions containing the inventive dyes added ineither the powdered or ball-milled microcrystalline state. It is clearlynot essential, however, to resort to the preparative complexities of dyemilling in order to achieve the desired spectral properties.

Example 4 Spectral Properties of Wet and Dried Dye DGD's.

Direct gelatin dispersions (DGD's) of Dyes 1-16 and Comparative Dyes A-Dwere prepared using powdered dye as described in Example C. Aliquots ofeach dispersion, held at 39° C., were transferred to 0.0032 cmpathlength glass cells and their absorption spectra measured immediatelyat 25° C. These samples are referred to in Table VIII as “wet DGD's”.Solution aliquots of each dispersion were also smeared onto standardglass microscope slides (0.8/1.0 mm thickness) to form uniformly thinwet films which were allowed to dry at ambient temperature and humidityfor at least 17 hours such that their D_(max) (dried) was less than 4.0absorbance units. The absorption spectra for these dried gelatin filmswere then measured at 25 C. These samples are referred to in Table VIIIas “dry DGD's”. The data are summarized in Table VIII.

TABLE VIII λ_(max) |_(max) DGD_(wet) DGD_(dry) Hbw Wet Hbw Dry Dye (nm)(nm) (nm) (nm) 1 793 794 18 22 2 738 737 19 35 3 558 559 12 14 3A 559560 12 14 4 779 781 24 35 4A 778 780 16 22 5 790 791 19 30 6 555 557 1719 7 785 788 17 21 8 721 719 40 44 8A 721 722 42 50 9 739 739 35 40 9A740 739 37 44 10 717 713 46 54 10A 762 772 50 52 10B 717 712 46 53 11751 757 34 49 12 758 763 29 44 13 554 554 15 21 13A 549 553 18 20 14 792794 20 23 15 723 724 41 45 16 771 771 48 59 A 682 684 75 82 Aa 686 68675 85 B 709 709 58 64 C 586 602 121 178 D 682 684 77 81

The above results clearly demonstrate that the useful spectral featuresof bathochromic absorbance maximum, narrow Hbw and high extinctioncoefficient for each inventive dye aggregated in wet aqueous gelatin,are largely retained in dried gelatin films or layers.

Example 5 Spectral Properties of Dried Gelatin Layers Containing DyesFormulated Using DGD and SPD Procedures.

Direct gelatin dispersions of the Inventive Dyes 2, 6, 8, 9, 11 and 15were prepared as described in Example C at concentrations equivalent todye laydowns of 0.064 mg/m². Solution aliquots of each dispersion weresmeared onto glass microscope slides (0.8/1.0 mm thickness) to formuniformly thin wet films which were then allowed to dry at ambienttemperature and humidity for at least 17 hours. The absorption spectrafor these dried films were then measured at 25° C. These samples arereferred to in Table IX as “dry DGD's”. The inventive Dyes 2, 6, 8, 9,11 and 15 were also dispersed in aqueous gelatin according to the SPDprocedure described in Example B. These SPD's were coated on a polyestersupport according to the following procedure. A spreading agent (Olin10G, an isononylphenoxy glycidol surfactand available from Olin Corp.)and a hardener (bis(vinylsulfonylmethyl)ether) were added to thedye-gelatin melt prepared as described above. A melt from this mixturewas then coated on a polytethylene terephthalate) support to achieve adye coverage of 0.064 g/m², a gelatin coverage of 1.61 g/m², and ahardener level of 0.016 g/m². The absorption spectrum of the dried SPDcoating was measured at 25° C. The data are summarized in Table IX.

TABLE IX λ_(max) Hbw DGD_(dry) DGD_(dry) λ_(max) SPD Hbw SPD_(dry) Dye(nm) (nm) dry^((nm)) (nm) 2 737 35 733 33 6 557 19 558 26 8 719 44 72047 9 739 40 735 58 11 757 49 751 51 13 554 21 552 25 13A 553 20 552 2515 724 45 719 48

The data show no significant differences in λ_(max) or Hbw for the driedgelatin films containing aggregated dyes formulated according to the DGDor SPD procedures outlined in Examples C and B, respectively.

Example 6 Process Removability of Dyes

The inventive Dyes 1-3, 5, 7-11, and 14-15 were formulated according tothe SPD procedure described in Example B. These dye dispersions werecoated on a polyester support according to the following procedure. Aspreading agent (surfactant 10G) and a hardener(bis(vinylsulfonylmethyl)ether) were added to the dye-gelatin meltprepared as described above. A melt from this mixture was then coated ona poly(ethylene terephalate) support to achieve a dye coverage of 0.161g/m², a gelatin coverage of 1.61 g/m², and a hardener level of 0.016g/m². The absorption spectrum of the dried SPD coating was measured at25° C. Identical elements were subjected to Kodak E-6® processing (whichis described in British Journal of Photography Annual, 1977, pp. 194-97)and the absorbance was measured for each. The results are shown in TableX.

TABLE X λ_(max)SPD_(dry) D_(max) Dye (nm) D_(max) after E-6 Processing 1790 >4.0 0.0 2 733 >4.0 0.0 3 558 2.8 0.0 5 758 >4.0 0.0 7 778 3.6 0.0 8720 2.5 0.0 9 735 3.3 0.0 10 705 3.1 0.0 11 751 >4.0 0.0 13 552 1.6 0.013A 552 1.3 0.0 14 784 >4.0 0.0 15 721 >4.0 0.0

In spite of the inordinately high optical (D_(max)'s) for the aggregatedcoated dyes, no residual deleterious dye stain (optical density) couldbe detected after processing.

Example 7 Dye Immobility and Thermal Stability

The inventive Dyes 1, 3, 9, 10 and 15 were formulated using the SPDprocedure described in Example B and coated on a polyester support asoutlined in Example 6. Each dye was coated at a laydown such that themeasured D_(max) was less than 3.5. For each example, the absorbancespectrum for the dyed gelatin coating was measured both before and afterincubation for seven days at 120° C./50% relative humidity. The resultsare summarized in Table XI.

TABLE XI D_(max) SPD Dye laydown λ_(max)SPD before D_(max) SPD after Dye(g/m²) (nm) incubation incubation 1 0.043 790 3.3 3.5 3 0.043 558 2.32.3 9 0.161 735 3.3 3.4 10 0.161 705 3.2 3.2 13 0.043 552 1.6 1.7 13A0.043 552 1.3 1.4 15 0.043 721 1.7 1.7

It is clear from the data that the aggregated dyes in the inventiveexamples show an excellent robustness toward high heat and humidity asevidenced by the fact that little or no density loss at the aggregateλ_(max) is observed as a result of incubation. Furthermore, the absenceof any detectable optical density at the monomeric λ_(max) of theinventive dyes following incubation demonstrates that little or nomobile monomeric dye species is produced under these conditions.Consequently, the aggregated inventive dyes exhibit excellent robustnessand fastness to diffusion at high temperature and humidity.

The invention has been described in detail with particular reference topreferred embodiments, but it will be understood that variations andmodifications can be effected within the spirit and scope of theinvention.

What is claimed is:
 1. A photographic element comprising at least onelight sensitive layer and at least one light insensitive layer andcontaining a dye of the Formula:

wherein X is oxygen or sulftir; R¹-R⁴ each independently represent ahydrogen atom or an unsubstituted or substituted alkyl group, anunsubstituted or substituted aryl group, other than a phenyl groupsubsitituted with a hydroxyl group, or an unsubstituted or substitutedheteroazyl group; L¹, L² and L³ each represents an unsubstituted methinegroup; M⁺ represents a proton or an inorganic or organic cation; and nis 0, 1, 2 or 3; and wherein the dye is in aggregated form and inaggregated form in an aqueous hydrophilic colloid medium has anabsorption halfbandwidth of less than 55 mn.
 2. A photographic elementaccording to claim 1, wherein at least one of R¹ and R² contains anionizable group, other than hydroxyl.
 3. A photographic elementaccording to claim 1, wherein R¹ and R² each independently represent aphenyl group substituted with an alkoxy, a carboxy or a sulfonamidogroup.
 4. A photographic element according to claim 1, wherein each ofR³ and R⁴ represent a hydrogen atom.
 5. A photographic element inaccordance with claim 1, wherein n is
 1. 6. A photographic elementaccording to claim 1, wherein n is
 2. 7. A photographic element inaccordance with claim 1, wherein the dye is in the light insensitivelayer and said layer comprises a hydrophilic colloid.
 8. A photographicelement in accordance with claim 7, wherein the hydrophilic colloid isgelatin.